CN108129624B - Molybdenum-phosphorus-nitrogen hybrid intumescent flame retardant and preparation method thereof - Google Patents
Molybdenum-phosphorus-nitrogen hybrid intumescent flame retardant and preparation method thereof Download PDFInfo
- Publication number
- CN108129624B CN108129624B CN201711476214.6A CN201711476214A CN108129624B CN 108129624 B CN108129624 B CN 108129624B CN 201711476214 A CN201711476214 A CN 201711476214A CN 108129624 B CN108129624 B CN 108129624B
- Authority
- CN
- China
- Prior art keywords
- molybdenum
- flame retardant
- phosphorus
- melamine
- phosphate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 48
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 46
- JVNCNCYJDLQGOI-UHFFFAOYSA-N [Mo].[P].[N] Chemical compound [Mo].[P].[N] JVNCNCYJDLQGOI-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 5
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 32
- QDAYJHVWIRGGJM-UHFFFAOYSA-B [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QDAYJHVWIRGGJM-UHFFFAOYSA-B 0.000 claims abstract description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 32
- 229920000877 Melamine resin Polymers 0.000 claims description 16
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 239000008098 formaldehyde solution Substances 0.000 claims description 15
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 15
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000002135 nanosheet Substances 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229920000388 Polyphosphate Polymers 0.000 claims description 4
- 239000001205 polyphosphate Substances 0.000 claims description 4
- 235000011176 polyphosphates Nutrition 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 3
- QVJYHZQHDMNONA-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1 QVJYHZQHDMNONA-UHFFFAOYSA-N 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- XZTOTRSSGPPNTB-UHFFFAOYSA-N phosphono dihydrogen phosphate;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(O)=O XZTOTRSSGPPNTB-UHFFFAOYSA-N 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 9
- 238000011065 in-situ storage Methods 0.000 abstract description 6
- 230000002195 synergetic effect Effects 0.000 abstract description 6
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 239000007789 gas Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
- C08G12/32—Melamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3009—Sulfides
Abstract
The invention discloses a molybdenum-phosphorus-nitrogen hybrid intumescent flame retardant and a preparation method thereof, and provides a synergistic intumescent flame retardant which integrates an acid source, a gas source and a carbon source into a whole and is formed by in-situ growth of a triazine ring polymer on the surface of nano molybdenum disulfide and molybdenum phosphate.
Description
Technical Field
The invention relates to the technical field of high-molecular flame retardance, and particularly relates to a molybdenum-phosphorus-nitrogen hybrid synergistic intumescent flame retardant and a preparation method thereof.
Background
Two-dimensional molybdenum disulfide is considered as a very promising inorganic nano flame retardant, but the flame retardant effect of the two-dimensional molybdenum disulfide used in polymers is not ideal. The common method is to simply mix molybdenum disulfide and other flame retardants and apply the mixture to a polymer, and although the flame retardant effect can be improved to a certain extent, the nano flaky molybdenum disulfide has poor compatibility with the polymer, cannot be well dispersed in a polymer material, and is difficult to well disperse, so that the mechanical property of a matrix polymer is damaged.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a molybdenum-phosphorus-nitrogen hybrid synergistic intumescent flame retardant and a preparation method thereof.
In order to achieve the purpose, the invention provides the following technical scheme:
the molybdenum-phosphorus-nitrogen hybrid intumescent flame retardant comprises the following components in percentage by mass:
12 to 15 percent of molybdenum disulfide
20 to 35 percent of melamine
40 to 60 percent of formaldehyde solution
9 to 20 percent of melamine phosphate
4 to 20 percent of molybdenum phosphate.
Preferably, the molybdenum disulfide nanosheet has fineness of 1000-.
Preferably, the concentration of the formaldehyde solution is 30% to 60%.
Preferably, the melamine phosphate is one or a combination of several of melamine cyanurate, melamine orthophosphate, dimelamine phosphate, melamine pyrophosphate and melamine polyphosphate.
Preferably, the molybdenum phosphate is an open framework or a compact structure with molecular sieves or zeolites.
A method for preparing the molybdenum-phosphorus-nitrogen hybrid intumescent flame retardant comprises the following steps:
(1) soaking molybdenum disulfide in phosphoric acid for 1-3 hours, and then washing with deionized water for 3-5 times;
(2) melamine and formaldehyde solution are put into a reactor, stirred at the speed of 300-500r/min and heated to 80 ℃, and after the mixed solution is completely transparent, the pH value is adjusted to 7-8 by 1M triethylamine;
(3) adding the molybdenum disulfide treated by the phosphoric acid, melamine phosphate and molybdenum phosphate into the solution obtained in the step (2) according to the proportion, stirring at the speed of 1000-1500r/min, controlling the temperature at 80 ℃ and the pH value at 7-8;
(4) after reacting for 5-8 hours, transferring the mixed solution obtained in the step (3) into an open container, dropwise adding phosphoric acid to adjust the pH value to 4-6, and then heating for 3-5 minutes by using microwaves;
(5) and taking out the cured sample, and crushing and grinding to obtain the molybdenum-phosphorus-nitrogen hybrid intumescent flame retardant.
The application aims to modify triazine polymer grafted on the surface of flaky molybdenum disulfide in situ and prepare the synergistic intumescent flame retardant by assisting the phosphate flame retardant, so that the mechanical property of the polymer is enhanced, and the advantages of small smoke generation amount and small toxic gas are achieved. The melamine resin with a triazine structure is selected to carry out in-situ crosslinking reaction on the surface of nano molybdenum disulfide to grow into an annular or cage-shaped structure, melamine phosphate and molybdenum phosphate are coated to form an integral structure, and a high-efficiency intumescent flame retardant integrating an acid source, a gas source and a carbon source is formed. The flame retardant mechanism is as follows: melamine phosphate and molybdenum phosphate are decomposed at about 200-300 ℃, the generated phosphoric acid catalyzes a matrix to form carbon, the generated nitrogen has no smoke toxicity, and the nitrogen can be used as a safe foaming agent to block oxygen, so that an excellent flame retardant effect is achieved, and the melamine phosphate and molybdenum phosphate can be widely applied to PP plastics and organic foam products. In order to facilitate use and transportation, the flame retardant and polypropylene can be compounded into flame-retardant master batches.
The invention has the following beneficial effects:
1. through reasonable design, melamine flame-retardant polymer components are successfully grafted and crosslinked in situ on the surface of two-dimensional molybdenum disulfide, and a truly synergistic intumescent flame retardant is prepared in a mode of in-situ reaction and cladding, so that the defects of each flame-retardant component are effectively overcome, the compatibility of the flame-retardant component with plastics is improved, the mechanical strength is enhanced, and the flame-retardant effect is obviously improved;
2. the method is simple and easy to implement and convenient for expanding production.
Detailed Description
In order to make the technical solutions of the present invention better understood, the following description is provided clearly and completely, and other similar embodiments obtained by those skilled in the art without creative efforts shall fall within the protection scope of the present application based on the embodiments in the present application.
Example 1:
the molybdenum-phosphorus-nitrogen hybrid intumescent flame retardant comprises the following components in percentage by mass:
12 percent of molybdenum disulfide
23 percent of melamine
50 percent of formaldehyde solution
Melamine orthophosphate 15%
5 percent of molybdenum phosphate
Wherein, the fineness of the molybdenum disulfide is 1000 meshes of nano-sheets, and the pH value is 7. The concentration of the formaldehyde solution was 30% (volume percent). The molybdenum phosphate has a molecular sieve type open framework structure.
A method for preparing the molybdenum-phosphorus-nitrogen hybrid intumescent flame retardant comprises the following steps:
(1) soaking molybdenum disulfide in phosphoric acid for 1 hour, and then washing with deionized water for 3 times;
(2) putting melamine and formaldehyde solution into a reactor, stirring at the speed of 300r/min, heating to 80 ℃, and adjusting the pH value to 7 by using 1M triethylamine after the mixed solution is completely transparent;
(3) adding the molybdenum disulfide treated by phosphoric acid, melamine phosphate and molybdenum phosphate into the solution obtained in the step (2) in proportion, stirring at the speed of 1000r/min, controlling the temperature at 80 ℃, and controlling the pH value to 7;
(4) after 5 hours of reaction, transferring the mixed solution obtained in the step (3) into an open container, dropwise adding phosphoric acid to adjust the pH value to 4, and then heating for 3 minutes by using microwaves;
(5) and taking out the cured sample, and crushing and grinding to obtain the molybdenum-phosphorus-nitrogen hybrid intumescent flame retardant.
Through thermogravimetric analysis, the initial decomposition temperature of the flame retardant is 255 ℃, the fastest thermal weight loss temperature is 375 ℃, the mass residue at 800 ℃ is 49%, and the mass residue at 1000 ℃ is 45.2%.
Example 2:
the molybdenum-phosphorus-nitrogen hybrid intumescent flame retardant comprises the following components in percentage by mass:
14 percent of molybdenum disulfide
Melamine 21.2%
Formaldehyde solution 46.2%
Dimelamine phosphate 15%
5 percent of molybdenum phosphate
Wherein, the fineness of the molybdenum disulfide is 2500 meshes of the nanosheet, and the pH value is 8. The concentration of the formaldehyde solution was 60% (volume percent). Molybdenum phosphate has a zeolite-type open framework structure.
A method for preparing the molybdenum-phosphorus-nitrogen hybrid intumescent flame retardant comprises the following steps:
(1) soaking molybdenum disulfide in phosphoric acid for 3 hours, and then washing with deionized water for 5 times;
(2) putting melamine and formaldehyde solution into a reactor, stirring at the speed of 500r/min, heating to 80 ℃, and adjusting the pH value to 7 by using 1M triethylamine after the mixed solution is completely transparent;
(3) adding the molybdenum disulfide treated by phosphoric acid, melamine phosphate and molybdenum phosphate into the solution obtained in the step (2) in proportion, stirring at the speed of 1500r/min, controlling the temperature at 80 ℃ and controlling the pH value at 8;
(4) after 7 hours of reaction, transferring the mixed solution obtained in the step (3) into an open container, dropwise adding phosphoric acid to adjust the pH value to 5, and then heating for 4 minutes by using microwaves;
(5) taking out the solidified sample, crushing and grinding to obtain the molybdenum-phosphorus-nitrogen hybrid intumescent flame retardant
Through thermogravimetric analysis, the initial decomposition temperature of the flame retardant is 245 ℃, the fastest thermal weight loss temperature is 346 ℃, the mass residue at 800 ℃ is 47%, and the mass residue at 1000 ℃ is 44.6%.
Example 3:
the molybdenum-phosphorus-nitrogen hybrid intumescent flame retardant comprises the following components in percentage by mass:
15 percent of molybdenum disulfide
Melamine 21%
40 percent of formaldehyde solution
8 percent of melamine polyphosphate
Melamine cyanurate 12%
4 percent of molybdenum phosphate
Wherein, the fineness of the molybdenum disulfide is 2000 meshes of nano-sheets, and the pH value is 9. The concentration of the formaldehyde solution was 50% (volume percent). The molybdenum phosphate has a compact structure.
A method for preparing the molybdenum-phosphorus-nitrogen hybrid intumescent flame retardant comprises the following steps:
(1) soaking molybdenum disulfide in phosphoric acid for 2 hours, and then washing with deionized water for 4 times;
(2) putting melamine and formaldehyde solution into a reactor, stirring at the speed of 400r/min, heating to 80 ℃, and adjusting the pH value to 8 by using 1M triethylamine after the mixed solution is completely transparent;
(3) adding the molybdenum disulfide, melamine polyphosphate, melamine cyanurate and molybdenum phosphate which are treated by phosphoric acid into the solution obtained in the step (2) according to the proportion, stirring at the speed of 1300r/min, controlling the temperature at 80 ℃ and the pH value at 7;
(4) after reacting for 8 hours, transferring the mixed solution obtained in the step (3) into an open container, dropwise adding phosphoric acid to adjust the pH value to 6, and then heating for 5 minutes by using microwaves;
(5) and taking out the cured sample, and crushing and grinding to obtain the molybdenum-phosphorus-nitrogen hybrid intumescent flame retardant.
Through thermogravimetric analysis, the initial decomposition temperature of the flame retardant is 251 ℃, the fastest thermal weight loss temperature is 360 ℃, the mass residue at 800 ℃ is 50.3%, and the mass residue at 1000 ℃ is 45.8%.
Comparative experiment:
the flame retardants obtained in examples 1, 2 and 3 and pure molybdenum disulfide were added to PP plastic in a proportion of 10% (mass percentage) for comparative experiments, and extrusion granulation was carried out to obtain flame retardant master batches. The oxygen index results are given in table 1 below:
TABLE 1
| Item | Example 1 | Example 2 | Example 3 | Adding molybdenum disulfide separately | Pure PP |
| Tensile Strength/N | 405 | 402 | 405 | 391 | 380 |
| Oxygen index/% | 29 | 28 | 29 | 20 | 17 |
The table shows that the flame retardant effect of the product of the embodiment on the matrix material is obvious, and the reinforcing effect is obvious, because the compatibility of the product of the embodiment and the matrix material is improved, the influence of poor dispersibility of molybdenum disulfide on the strength of the composite material is effectively compensated.
The invention provides a synergistic intumescent flame retardant which integrates an acid source, a gas source and a carbon source and is formed by in-situ growth of a triazine ring polymer on the surface of nano molybdenum disulfide and molybdenum phosphate.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (5)
1. The molybdenum-phosphorus-nitrogen hybrid intumescent flame retardant is characterized by comprising the following components in percentage by mass:
12 to 15 percent of molybdenum disulfide
20 to 35 percent of melamine
40 to 60 percent of formaldehyde solution
9 to 20 percent of melamine phosphate
4 to 20 percent of molybdenum phosphate
The method for preparing the molybdenum-phosphorus-nitrogen hybrid intumescent flame retardant comprises the following steps:
(1) soaking molybdenum disulfide in phosphoric acid for 1-3 hours, and then washing with deionized water for 3-5 times;
(2) melamine and formaldehyde solution are put into a reactor, stirred at the speed of 300-500r/min and heated to 80 ℃, and after the mixed solution is completely transparent, the pH value is adjusted to 7-8 by 1M triethylamine;
(3) adding the molybdenum disulfide treated by the phosphoric acid, melamine phosphate and molybdenum phosphate into the solution obtained in the step (2) according to the proportion, stirring at the speed of 1000-1500r/min, controlling the temperature at 80 ℃ and the pH value at 7-8;
(4) after reacting for 5-8 hours, transferring the mixed solution obtained in the step (3) into an open container, dropwise adding phosphoric acid to adjust the pH value to 4-6, and then heating for 3-5 minutes by using microwaves;
(5) and taking out the cured sample, and crushing and grinding to obtain the molybdenum-phosphorus-nitrogen hybrid intumescent flame retardant.
2. The molybdenum-phosphorus-nitrogen hybrid intumescent flame retardant of claim 1, which is characterized in that the molybdenum disulfide has nanosheets with fineness of 1000-2500 meshes and pH value of 7-9.
3. The molybdenum-phosphorus-nitrogen hybrid intumescent flame retardant of claim 1, wherein the concentration of the formaldehyde solution is 30% -60%.
4. The molybdenum-phosphorus-nitrogen hybrid intumescent flame retardant of claim 1, wherein the melamine phosphate is one or a combination of melamine orthophosphate, dimelamine phosphate, melamine pyrophosphate and melamine polyphosphate.
5. The molybdenum phosphorus nitrogen hybrid intumescent flame retardant of claim 1, wherein the molybdenum phosphate is an open framework or a compact structure with molecular sieves or zeolites.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711476214.6A CN108129624B (en) | 2017-12-29 | 2017-12-29 | Molybdenum-phosphorus-nitrogen hybrid intumescent flame retardant and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711476214.6A CN108129624B (en) | 2017-12-29 | 2017-12-29 | Molybdenum-phosphorus-nitrogen hybrid intumescent flame retardant and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108129624A CN108129624A (en) | 2018-06-08 |
| CN108129624B true CN108129624B (en) | 2020-03-27 |
Family
ID=62393718
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711476214.6A Active CN108129624B (en) | 2017-12-29 | 2017-12-29 | Molybdenum-phosphorus-nitrogen hybrid intumescent flame retardant and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108129624B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109942891B (en) * | 2019-03-12 | 2020-03-06 | 江南大学 | Phosphorus-nitrogen-zinc two-dimensional supermolecule coated molybdenum disulfide hybrid flame retardant and application thereof |
| CN114106466B (en) * | 2020-08-26 | 2023-12-12 | 合肥杰事杰新材料股份有限公司 | Low-combustion-heat low-smoke halogen-free flame-retardant polypropylene composite material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4187377A (en) * | 1977-06-17 | 1980-02-05 | Asahi Glass Company, Ltd. | Halogen-containing s-triazine compound |
| JPS5624423A (en) * | 1979-08-03 | 1981-03-09 | Kanegafuchi Chem Ind Co Ltd | New polymer havine triazing ring and its preparation |
| CN103819735A (en) * | 2014-03-03 | 2014-05-28 | 中国科学院青岛生物能源与过程研究所 | Inflatable graphite/melamine salt synergic intumescent flame retardant and preparation method thereof |
-
2017
- 2017-12-29 CN CN201711476214.6A patent/CN108129624B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4187377A (en) * | 1977-06-17 | 1980-02-05 | Asahi Glass Company, Ltd. | Halogen-containing s-triazine compound |
| JPS5624423A (en) * | 1979-08-03 | 1981-03-09 | Kanegafuchi Chem Ind Co Ltd | New polymer havine triazing ring and its preparation |
| CN103819735A (en) * | 2014-03-03 | 2014-05-28 | 中国科学院青岛生物能源与过程研究所 | Inflatable graphite/melamine salt synergic intumescent flame retardant and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| The influence of melaminephosphate modified MoS2 on the thermal and flammability of poly(butylene succinate) composites;Keqing Zhou et al.;《Polym.Adv.Technol.》;20160512(第27期);1397-1400 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108129624A (en) | 2018-06-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108129624B (en) | Molybdenum-phosphorus-nitrogen hybrid intumescent flame retardant and preparation method thereof | |
| CN107987320B (en) | A kind of aza synergistic expanding fire retardant of phosphorus and preparation method thereof | |
| CN113025002B (en) | Degradable foaming material and preparation method thereof | |
| CN103012904B (en) | Halogen-free flame-retardant master batch | |
| CN101134830A (en) | Non-bittern expanding flame-proof material and method for making same | |
| CN102127230A (en) | New process for preparing modified melamine polyphosphate | |
| CN108424547B (en) | Hybrid modified melamine salt, preparation method and application thereof | |
| CN110563944B (en) | Polyphosphazene covalent triazine polymer and preparation method and application thereof | |
| Tian et al. | Effect of char-forming agents rich in tertiary carbon on flame retardant properties of polypropylene | |
| de Souza et al. | Recent development on flame retardants for polyurethanes | |
| KR101534268B1 (en) | Manufacturing method of recycle resistance to flame polyurethane foam | |
| CN109438840A (en) | A kind of wear-resisting flame-retarded plastic and preparation method thereof | |
| CN110128741B (en) | Polyolefin foam material and preparation method thereof | |
| CN108084660B (en) | A kind of expansion type fire retarding epoxide resin and preparation method thereof | |
| CN107163076B (en) | Phosphorus-Containing Triazine salt compound and its preparation method and application | |
| CN114806023A (en) | Foaming material for floating equipment and preparation method thereof | |
| CN106118022B (en) | Thermoplastic plastic flame retardant, flame-retardant thermoplastic plastic and preparation method | |
| CN108559133A (en) | A kind of preparation method of diatom soil matrix inorganic-organic hybridization fire retardant | |
| KR20160027422A (en) | Method of manufactuaring insoluble sulfur | |
| JP2019521233A (en) | PBS resin composition and method for producing the same | |
| CN112175404A (en) | Preparation method of bamboo charcoal-based high-flame-retardance expansion type synergistic system | |
| CN107324305B (en) | Production method of inorganic ammonium salt, inorganic ammonium salt and application | |
| de Souza et al. | Aluminum hypophosphite–based highly flame-retardant rigid polyurethanes for industrial applications | |
| CN111825972A (en) | Flame-retardant polyurethane foam plastic for underground coal mine and preparation method thereof | |
| Hou et al. | Metal-organic frameworks as promising flame retardants for polymeric materials |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A molybdenum phosphorus nitrogen hybrid flame retardant and its preparation method Granted publication date: 20200327 Pledgee: Qingdao High-tech Zone High-tech Microfinance Co.,Ltd. Pledgor: QINGDAO DECHUANG NEW MATERIAL CO.,LTD. Registration number: Y2024980011774 |